Method for producing copper-containing hydrogenation catalysts



United States Patent 8 Claims. (61. 252-454) This application is acontinuation-in-part of our copending application Serial No. 4,231,filed January 25, 1960, now abandoned.

This invention relates to a process for producing coppercontainingcatalysts suitable for the selective hydrogenation of oils and fats.

The catalytic behavior and function of copper catalysts in hydrogenationhave been studied for a long time by many investigators and a number ofpublications have been made concerning methods for producing suchcatalysts.

When the proposed catalysts are compared with each other in regard totheir catalytic activity for selective hydrogenation purposes, it can besaid that the most active is Adkins catalyst. Difficulties areencountered, however, in obtaining uniform activity of the saidcatalyst. Only selected catalysts having the highest level of theactivity can be used for selective hydrogenation of oils and fats. Thisis because, in such hydrogenation, there are presumably moreopportunities for the catalyst to be poisoned due to the inherentconditions of selective hydrogenation, e.g., low hydrogen pressure, agreater amount of impurities in the material being hydrogenated, etc.,than in other types of hydrogenation, and these conditions impose severerequirements in regard to the uniformity and life of the catalyst used.Thus, it is important to improve the char- 3,1914% Patented July 27,1965 ice life without impairing the inherent characteristics of copperitself for hydrogenation purposes.

According to the present invention a copper-containing hydrogenationcatalyst is produced by a process which consists essentially of reactingan aqueous acidic solution with an aqueous alkaline solution, saidaqueous acidic solution containing copper ions and ions of a secondmetal selected from the group consisting of zinc, cadmium, aluminum,silicon, titanium, tin, zirconium, vanadium, chromium, molybdenum,tungsten, manganese, Ag, Sc, Y, La, Ce, Ga, In, Hf, Be, Mg, Ca, Sr, Baand metals of Group VIII of the Mendeletf Periodic Table, the mol ratioof said second metal to copper in said acidic solution being between1:100 and :30. It is preferable to keep the mol ratio of nickel tocopper between 1:100 to 5:95. It is of critical importance in theinvention that said acidic and alkaline solution be reacted by addingthem simultaneously to a third aqueous solution having a pH of between 7and 11 to form a combined precipitate, the rate of adding said acidicand alkaline solutions to said third aqueous solution being so regulatedas to keep the pH of the reaction mixture between x0.5 and xl0.5(wherein x is from 7 to 11) throughout the entire duration of thereaction. After the reaction is completed the precipitate is washed withWater to remove the alkali therefrom and then same is dried, whereby analkali-free, hydrogenation catalyst is obtained. It is preferable tocarry out the reaction at an elevated temperature, such as 60 degrees todegrees centigrade.

The catalyst produced by the process of this invention is particularly,although not exclusively, suitable for the selective hydrogenation ofoils and fats.

The following Table I is a comparison between catalysts preparedaccording to the present invention and catalysts prepared according tothe prior art methods.

TABLE I.HYDROGENATION OF REFINED FINBACK WHALE OIL Amount of thecatalyst- Iodine Number of hydrogenated Catalyst percent by weight ofoil at selected times during the the oil hydrogenation Percent PercentNo Type of catalyst based on based on 1 hr. 2hrs. 3hrs. 4hrs. 5hrs.

weight of Weight of catalyst metal 1 1 Copper 5.0 2. 4 104. 2 92.1 83. 578. 4 78.2

2"- Adkins 2. 0 2. 0 78.5 71.8 69. 5 69. 2 69. 1

3-.. Oopper-chromium 10. D 10. 0 85. 4 79. 5 78. 6 78.0 77. 8

4.-. Copper-chromium 5- Copper-chromium 6 Copper-chromium 7.--Copper-aluminum 8 Copper-zinc (8:2) 2 1. 5 0.8 87. 4 76. 8 74. 0 70. 570. 1

Notes:

(1) Hydrogenation Conditions: In all cases, refined finback whale oil ofAcid Number 0.21 and Iodine Number 108.9 was hydrogenated attemperatures between degrees and 200 degrees centigrade under normalhydrogen pressure.

(2) 1 Roughly estimated as metal oxide.

(3) 2 Figures in the parentheses indicate the mol ratio between themetals.

acteristics of catalysts for carrying out selective hydrogenationcommercially and successfully.

An object of this invention is to provide a method for producingcopper-containing hydrogenation catalysts which are comparable to Adkinscatalyst and which have high and uniform activity as well as a longuseful catalytic Catalyst No. -1 was prepared according to thewell-known method described at page 24 or 36, Vol. 68 (1948) of theJournal of the Pharmaceutical Society of Japan. Catalyst No. 2 wasprepared according to the method described at page 878, Vol. 26 (1934)of Industrial and Engineering Chemistry. The fundamental principle ofselective hy- U drogenation of oils and fats is to hydrogenate andconvert polyunsaturated constituents to monounsaturated constituentswithout causing anyhydrogenation of the previously .existingmonounsaturated constituents. theoretical considerations, the limit ofselective hydrogenation of finback whale oil is between 69 and 70,expressed as Iodine Number. From an examination of Table I, it canbeseen that the most active catalyst is Adkins catalyst and the resultsshow that the Iodine Number of the hydrogenated oil decreases rapidlyand finally meets the theoretical value when it is used. On the otherhand, the catalysts produced by prior art methods exemplified in Nos. 1,3 and 4 in Table I and comprising copper alone or binary catalysts ofcopper and chromium show less catalytic activity as illustrated by thedata showing their incomplete eifect in decreasing the Iodine Number ofthe hydrogenated oil. In addition, practically nodifference in catalyticactivity is observed between the catalyst No. 1 comprised of copperalone and the binary catalysts Nos.

3 and 4 comprised of copper and chromium.

Catalysts Nos. 5 to 8 are the catalysts made according to the inventiondescribed above and further described hereinafter and, manifestly, thesecatalysts are highly active and have a long life.

Generally, the active portion of the copper-containing catalysts 1-8 isobtained as a precipitate, which may or may not be adhered todiatomaceous earth or other carriers, by reacting two kinds ofsolutions, one a solution (hereinafter referred to as the A solution)which is acidic and contains copper ions alone or copper and secondmetal ion(s) and the other an alkaline solution (hereinafter referred toas the B solution).

Catalyst No. 3 was made by reacting the A and B solutions by pouring theA solution into the B solution. From experimental observations likethose listed above, it has been understood that the principal effect ofselective hydrogenation is given by the copper alone and the secondmetals, such as chromium and others, merely serve as carriers for thecopper.

We have discovered highly useful improvements of critical importance inthe method of producing copper binary catalysts by precipitation, one ofwhich is to control the reaction conditions so as to keep the pH ofthe'reaction mixture between x-0.5 and x'+0.5 (wherein x is from 7 to11) throughout the entire duration of the reaction. A further criticaland chief feature of this invention is more specifically described bythe following. When a solution containing copper and second metal ionsis reacted with an alkali solution to produce a co-precipitate, which iseither adhered 'to diatomaceous earth or not adhered to any carrier, theessential step in carrying out the invention is to simultaneously addboth the A and the B solutions to a third liquid, such as water, whichis strongly agitated and whose'pI-I is adjusted before addition of the Aand B solutions to between 7 to 11 and is maintainedduring From " metalsto copper should be more than 1:100 expressed in mols and if this molratio becomes less than 70:30, the activity of the catalyst graduallydecreases.

In case a metal having the inherent property to hydrogenate oil and fat,such as nickel, is combined with copper,

the mol ratio thereof to copper should be less than 5,295

and should be more than 1:100. The following are examples illustratingthe invention:

Example 1 I A solution containing 6.35 g. of cupric ion and 5.20 g. ofchromic ion was prepared as the A solution by dissolving their sulfatesin 100ml. of water. The B solution was prepared by dissolving 29 g. ofsodium carbonate in 120 ml. of water. 10 g. of diatomaceous earth weresuspended in 200 ml. of water, which suspension was heated and held at70-80 degrees centigrade and then the pH was adjusted to 9 using causticsoda solution. The A and B solutions were simultaneously added to theabove hot suspension in such a manner as to keep the pH of thesuspension between 8.5 and 9.5. After the reaction was comple ted, theproduced precipitate was filtered and washed with Water until thefiltrate became slightly alkaline or neutral, thenthe filter cake wasdried and pulverized.

This product was the catalyst No. 5 in Table I.

and after the reaction in the range of -x0.5 and x+0.5, 0

wherein x is from 7 to 11, by controlling the rate of-adding both the Aand the B solutions. by thus reacting the solutions is washed with wateruntil no or very little indication of alkali is observed 'in thefiltrate of the washings, then it is dried and pulverized, if

necessary, and utilized as the catalyst. served in the activity of theproduced catalyst by converting the precipitate to oxide form, either byblowing air into the reaction solution containing the precipitatessuspended The precipitate formed As a comparison for the above-describedmethod, catalyst No. 4 was prepared by pouring the A solution into the Bsolution, which was held previously at 70-80 degrees centigrade andwhich contained 10 g. of diatomaceous earth suspended therein. Then, theresulting precipitate was washed until neutral, dried-and pulverized.

Example 2 A solution containing 5.72 g. of cupric ion and 0.52 g. ofchromic ion, was prepared by dissolving their sulfates in 60 ml. ofwater. This formed the A solution. A 20% sodium carbonate solution wasprepared as the B solution.

Separate from the A and B solutions, 5 g. of diatomaceous earth weresuspended in ml. of water and the pH of this suspension was adjusted to8. Next the suspension was vigorously agitated, then the A and Bsolutions were simultaneously added to the suspension so that theneutralization reaction was kept at a pH of between 8.5 and 9.5. Theproduced precipitate. was filtered and washed,

' then dried and pulverized. The catalyst thus obtained was catalyst No. 6 in Table 1.

Example 3 "60 ml. of an aqueous solution, containing 6.35 g. of

. cupric ion and 2.70 g. of aluminum ion dissolved from their sulfateswas prepared as the A solution. An aqueous sodium carbonate solution of20% concentration was prepared as the B solution. The remainder of theprocedure No harm is ob 1 was carried out exactly as in Example 2, andcatalyst No. 7

was obtained.

Example 4 60 ml. of an aqueous'solution, containing 5.09 g. of cupricion and 1.31 g. of zinc ion dissolved from ther sulfates, was preparedas the A solution, and a 20% aqueous solution of sodium carbonate wasprepared as the B solution. The remainder of the procedure was carriedout exactly as in Example 2, and the catalyst No. -8 was obtained.

Example5 Catalyst'No. '5, prepared as in Example 1, was roasted catalystNo. 9-wasthus obtained.

Example 6 The procedures of Example No. 2 and then Example No. 5 werefollowed and catalyst No. was obtained.

Thus, the features of the invention are simple, yet they 'bring aboutfar better products when compared with products of already knownprocesses wherein the A solution is neutralized with B solution or the Aand B solutions are mixed without any specification whatsoeverconcerning the manner of carrying out the reaction steps or the TABLEIII.HIGH PRESSURE HYDROGENATION OF COCONUT OIL FATTY ACID ESTER TOPRODUCE A FATTY ALCOHOL Amount of the Catalyst Products No. CatalystPercent Percent Time re- Acid Saponias the as the quired for NumficationAcetyl Catalyst Metal hydrogenaber Number Number Oxide tion 1 Adkins r 66 8% hr 0.46 13. 1 207 2 Copper-Chromium (1:1)+1+2 l 6 3. 5 is hr 0. 389. 3 210 3..- Copper-Chromium (911)+:+z- 6 3. 5 as 111 0. 41 10.2 208Note s: (1) Methyl Ester of Coconut Oil Fatty Acid:

Acid Number 0.58, Saponification Number 250, Iodine Number 9.46. (2)Hydrogenation Condition: In all cases initial hydrogen pressure at roomtemperature was 120 Kg/em and the maximum reaction temperature was keptat 320 degrees centigrade, (3) Figures in the parentheses indicate themol ratio between the metals. (4) Catalysts are produced as describedinExamples 5 and 6, catalysts No. 9 and No. 10, respectively.

conditions under which they are reacted. It is thought, as the reasonfor the highly stabilized catalytic activity of catalysts made by themethod of the present invention, that the above-described steps of theinvention bring the copper and combining metal precipitate into a morein timately combined state and structure, which has not been possiblewith the prior art processes and this characteristic combination andstructure improves the catalytic activity of the catalyst forhydrogenation purposes.

The catalytic function of catalysts produced by the invention issomewhat different than that of the simple copper catalysts. This isderived from the fact that there is only a very slight increase in theamount of solid fatty acids, particularly, iso-oleic acid, in oil andfat hydrogenated by catalysts produced according to the invention.However, the hydrogenated oil and fats are satisfactory for industrialpurposes as shown in Table II.

TABLE II.SODID FATTY ACID CONTENT IN HYDRO- GENATED FINBACK WHALE OILWhen catalysts prepared according to the invention are used for purposesother than selective hydrogenation of oils and fats, the catalyticactivity compares well with that Example 7 An A solution was prepared bydissolving 4.2 g. of Cu(NO' .3H O and 1 g. of H PtCl in 50 ml. of water.The B solution was a 10% sodium carbonate solution. 6.3 g. ofdiatomaceous earth were suspended in ml. of water, and obtainedsuspension was heated and held at 70-80 degrees centigrade and then thepH was adjusted to 8.5 using the B solution. The A and B solutions weresimultaneously added to the above hot suspension in such a manner as tokeep the pH of the suspension between 8.0 and 9.0 throughout the entirebody of the reaction mixture and for the entire duration of thereaction.

After the reaction was completed, the produced precipitate was filteredand washed with water until the filtrate became neutral and chloride ionfree, then the filter cake was dried and pulverized. This product wasthe catalyst No. 11 in Table IV.

Example 8 An A solution was prepared by dissolving 6.04 g. of cupric ionand 0.29 g. of nickel ion in the form of their sulfates in 100 ml. ofwater. The B solution was 10% sodium carbonate. 6.3 g. of diatomaceousearth were suspended in 100 ml. of water, and the obtained suspensionwas heated and held at 70-80 degrees centigrade and then the pH wasadjusted to 9.0. The A and B solutions were simultaneously added to theabove hot suspension in such a manner as to keep the pH of thesuspension between 8.5 and 9.5 throughout the entire duration of thereaction and entire body of the reaction mixture. After the reaction wascompleted, the produced precipitate was filtered and washed with wateruntil the filtrate became neutral, then the filter cake was dried andpulverized. This product was the catalyst No. 12 in Table IV.

Example 9 An A solution was prepared by dissolving 4.42 g. of CuSO .SH Oand 0.50 g. of 080 in 34 ml. of water. The B solution was prepared bydissolving 2.71 g. of sodium nitrate in 34 ml. of 10% sodium carbonate.1.49 g. of diatomaceous earth were dispersed in 100 ml.

of water, and obtained suspension was heated and held at 7080 degreescentigrade and then the pH of the suspension was adjusted to 8.5 byusing sodium carbonate. The A and B solutions were simultaneously addedto the above hot suspension in such a manner as to keep the pH of thereaction mixture between 8.0 and 9.0 through; out the entire body of thereaction mixture and entire duration of the reaction. After the reactionwas completed, the produced precipitate was filtered and washed withwater until the filtrate became nitrate and sulfate ion free, then thefilter cake was stored in ethanol. This product was the catalyst No. 13in Table IV.

TABLE IV 8' V to 110 degrees centigrade for3 hours, and then pulverized.The obtained powder was catalyst No. 14.

Example 1'] hydrogenation Composition of C1 =fatty acid during IodineNumber Hydrogenating Time On.)

Saturated f.a., percent Monounset. f.a., percent Catalyst No.

Di-unsat. f.a., percent Transisomer, percent Refined cotton seed oil washydrogenated by using 1 (wt) percent of hydrogenation catalysts Nos. 11,12, and 13 at 180 degrees centigrade under atmospheric pressure withhydrogen, and the results are shown in Table IV.,

Example 10 An A solution was prepared by mixing 500 ml. of coppersulfate solution and 500 ml. of a chromium sulfate solution. The coppersulfate solution was prepared by dissolving 249.7 g. of copper sulfate(CuSO .5H' O) in 1,000 ml. of water, and the chromium sulfate solutionwas prepared by dissolving 358.3 g. of chromium sulfate (Cr (SO .l8H O)in 1,000 ml. of water. i

The B solution was a percent sodium carbonate (Na CO solution. 7

200 ml. of water were heated to 95 degrees centigrade and then the Bsolution was poured into the water until the pH of the obtained thirdsolution was adjusted to 9.0. Under strong agitation, the A and Bsolutions preheated to 95 degrees centigrade were then continuouslyflowed into said third solution at such a rate as to keep the pH of thereaction between 9.0 and, 9.2 and the temperature of the reactionmixture at 90 degrees to 95 degrees centigrade. The reaction mixture wasstirred for 15 minutes at 90 degrees to 95 degrees centigrade and thenallowed to settle.

The mother liquid was taken off by decantation and the precipitate waswashed with hot water (80 to 90 C.) until the washings became negativeto phenol- -phthalein. The precipitate was filtered and the obtainedfilter cake was dried in an air oven kept at 105 degrees Exactly thesame procedure as used for the preparation of catalyst No. 14 (Example7) was followed and the obtained powder was catalyst No. 15.

Table V shows the results achieved by catalystsNo. 14 and No. 15. Arefined and deodorized cotton seed salad oil was used as the oil' to behydrogenated. The oil had an Iodine Value 111.5, Saponification Value195.6 and Acid Value 0.22.

TABLE V.'CHANGE OF IODINE NUMBER BY HYD R0 GENATION Catalyst No 14 15Cu/Cr Ratio, 1/1 7 3/1 Amount of Catalyst (percent by weight 1 based onweight of oil) 1 2 Note: Y i h HydrogenationOondition: Reactiontemperature was kept at from to'205 degrees centigradeandreaction'pressurewas atmospheric pressure Example 12 Table VI showsthe examples of preparations of various copper binary catalysts of thisinvention according to the same procedure illustrated in Example 1, andthe results of hydrogenations of cotton seed oil using these catalystsat 200 degrees centigrade and under normal hydrogen pressure.

TABLE VL-PREPARATIONS OF VARIOUS COPPER BINARY CATALYSTS AND HYDROGENATIONS OF COTTON SEED OIL THEREBY Concentration percent oil duringhydrogenation using several of th shown in Table VI.

m m o "IIIIIIII s w B m m ILIIILITIL m .ZLLLLQZLLIL LLLLLITTT: AOOOOOOOOOO OO OOOOOOROOOO O H wm fi mo0 0 0 0 w0w Maammwmaamaaaaamwmmwmmmawwmaaoaoaaa NNNNNNNNNNNNNNNNNNNNNNNNNNKNKNNCmmmmmmmmmmmmmmmmmmwmmmmmmmmmmw m a 1111111111111111111111111 111111 1 :1m W/\ A mmmmwwwmmflwnmmww%wwmmamwmmwwmmm gLKZ&&&T&2.&&L&L320.0.QQQQQQLLZZZZ 2 w m m II m s n I: m n I: u M m II mm m m :3 m m m n .N 0 m 5m ml: n F mmnmu swim m 3 m 0 m N @0000 Nm mm sm m m m mm mw .1 A A0 mTmH MomBN 77 An Am x F 777 7 mm m nmmnn mmmmm anw m c m M m H a C m m 0. o F m m m u C m m 0 MN C s 4 e catalysts TableVII shows typical examples of fatty acid composition of C acids in thehydrogenated cotton seed TABLE VL-PREPARATIONS OF VARIOUS COPPER BINARYCATALYSTS LAND HYDRO COTTON SEED O-IL ILHEREBY GENAmIONS OF n h n m s BLL w m +0... 4704511529485224976861490214871 e r 801L59-7 047297126596769934 32 D & S97776%w %787887876666666676H78E m m m m 1n 4 rm.m d .D m m 9 1 mm. 9318446685325446330286700721008 O 5 O om Znmom 4nnm0 7 3 o w&7 Z5 m7 7 &5 m mm 997%776&878%Mw9%%7767666W7767787 0 0 m nh 3 r. d 8 M d t n m u en d wen 9333130268138983160565559305216 n UQILLQQO omifliiQQk- LiLQZLQKQQO 2 L a Wd an 9 0 8888m89898998oo8778H77778 Mfinvs r. C h h .1 wu O 2 0 2 0 u N n m8059695828138120213783409250313 0 68291346 358634097174313139510 h00909089%W099099988988899989909 a O .11 l 1 1 1s 1. l w 1 m g 1 m y Hffl fl 0000000000000000000000000000000 WW. 10w22222222222Z2Z2ZZ2LLLLLLL2ZZZ22 um mh mm n 0 mm M A P557055555555-U555FJ55555V0555555VJ55 fififififififi fifififififififl H009000000000U0U%000000000000000 1 m P Qm9999999979999999999999 1 m 1 .Wm S d 000000000000000000000000 M mmmmmmmv 87777777777787778888887 T mk me T w a V- 1 a t a C TABLE VIL-COMPOSITION F om FATTY ACIDS DURINGCatalyst 52 was preliared from the same Solutions as HYDROGENATIONcatalyst 51 but follow-mg the same procedures as for catalysts 48 and50. Iodine Saturated Monounsat- Di-ui isgt- Catalysts 4752 all werewashed with distilled water Number (Pemmt) 3 53 23, 35 until they becamenegative to phenolphthalein.

.Hydrogenation using Catalysts 47-53. 16 was an A refined and deodorizedcottonseed salad oil having 99.9 v 3.3 41.5 an Iodine Value of 111.5,Saponification Value of 195.6 33:: 3:; and an Acid Value of 0.22. Thehydrogenation tempera- 84.2 3.1 65.8 31.1 ture was from 195 to 205degrees centigrade. 21 10M 34 4 4L 6 0 The following table lists theresults.

80.3 V 7 4.5 Catalysts No. 47 and No.48, No. 49 and No. 50, and '29:? 3:7 No. 51 and No. 52 are directly comparable because the 66.1 3.3 92.54.2 same solutions were used and only the mixing methods 31 9M) 5 537428 Were different. In each case the catalysts made using the 87.3 3.462.1 34.5 .third solution (Nos. 48, 50 and 52) are unexpectedly 83.6 3.466.4 30.2 C t1 t f h p 81.4 3.2 69.5 27.3. more active. 3 ayst 7 isinactive or ydrogenating 79.2 3.3 72.3 24.4 cottonseed oil because itcontains alkali. 42 5 4 65.3 It is to be understood that'theinvention isnot limited 70.3 33. 1 1%- g to the specific details of the examplesherein described but 22 can be practiced in other ways without departurefrom 64.0 3.3 94-6 the spirit and scope of the invention as defined inthe appended claims.

RESULTS or HYDRO GENATIQN Catalyst Now; 47 4s 49 I 50 I 51 I 62 .53

Amount of Catalyst: (Pen 1 1 1 2 2 1/1 1/1 1/1 3/1 3/1 3/1 11 Free FreeFree Free Free Added Hydrogenation (Figures in Iodine Value):

Example 13' What is claimed is:

For the purpose of showing the unexpected improvements which result frommixing of the A and B solutions with a third solution, whose pH iscontrolled, the following tests'were conducted.

Preparation of catalyst without using the third soluti0n.Catalysts 47and 49 were prepared by directly mixing together A and B solutions,prepared in accordance with Example 10 and held at 95 degrees centigradeso that the pH of the reaction solution was maintained from 9.0 to 9.2;

Catalyst 47 was prepared from 200 ml. A solution and 250 ml. B solution.Catalyst 49 was prepared from 200 ml. of the A solution diluted withdistilled water to 600 ml. and 350ml. of the B solution diluted to 1400ml.

Catalysts 51 and 53 were prepared by directly mixing together A and Bsolutions prepared in accordance with Example 11 held at 95 degrees sothat the pH of the reaction solution was maintained at from 9.0 to 9.2.Catalysts 51 and 53 were prepared from 320 ml. of the A solution and 250m1. of the B solution. After washing and drying, 10 m1. of distilledwater were mixed with sodium hydroxide (20 mg. calculated as K 0) andsuch was mixed with 5 g. of catalyst 53.

Preparation of catalyst using the third s0luti0n.Catalysts 48 and 50were prepared from the same solutions as catalysts 47 and 49,respectively. The sole difierence was that the A and B solutions wereadded to a third solution consisting of distilled water to which Bsolution was added until the third solution had a pH of 9. Then the Aand B solutions were simultaneously added to the .third solution.

1. A process of producing a copper-containing hydrogenation catalyst,which consists essentially of reacting an aqueous acidic solution withan aqueous alkaline solution capable of reacting with the acidicsolution to form a coprecipitate of the hereinafter mentioned metals,said aqueous acidic solution containing copper ions and ions of a secondmetal selectedfrom the group consisting of zinc, cadmium, aluminum,silicon, titanium, tin, zirconium, vanadium, chromium, molybdenum,tungsten, manganese, Ag, Sc, Y, La, Ce, Ga, In, Hf, Be, Mg, Ca, Sr, Ba,and metals of Group VIII of the Mendelefl Periodic Table, the mol ratioof said second metal to copper in said acidic solution beingbetweenlzlOO and 70:30, said acidic and alkaline solutions being 'addedsimultaneously to an aqueous third solution having a pH between .7 and11 to form a combined precipitate ofsaid metals, the rate of adding saidacidic and alkaline solutions to said third aqueous solution being soregulated asto keeputhe pH of the reaction mixture between xO.4 andx+0.5 (wherein x is from 7 to 11) throughout the entire duration-of thereaction, washing the precipitate with iwate rto remove the alkalitherefrom and then drying the same, 'wherebyan alkali-free hydrogenationcatalyst is obtained. l

2,. A process of producing a copper-containing catalyst for the'hydrogenationof oils and fats which consists essentially of reacting anaqueous acidic solution with an aqueous. alkaline solution containing atleast one .alkali selected from the group consisting of hydroxides andcarbonates of alkali metals and'calcium hydroxide and mixtures thereof,said aqueous acidicsolution containing 'copper ions and ions of a secondmetal selected from the group consisting of Zinc, cadmium, aluminum,silicon, titanium, tin, zirconium, vanadium, chromium, molybdenum,tungsten, manganese, Ag, Sc, Y, La, Ce, Ga, In, Hf, Be, Mg, Ca, Sr, Baand metals of Group VIII of Mendelefi? Periodic Table, the mol ratio ofsaid second metal to copper in said acidic solution being between 1:100and 70:30, said acidic and alkaline solutions being added simultaneouslyto an aqueous third solution having a pH between 7 and 11 to form acombined precipitate of said metals, the rate or adding said acidic andalkaline solutions to said third aqueous solution being so regulated asto keep the pH of the reaction mixture between x0.5 and x+0.5 (wherein xis from 7 to 11) throughout the entire duraton of the reaction, thereaction being carried out at 60 degrees to 90 degrees centigrade,washing the precipitate with water to remove the alkali therefrom andthen drying the same.

3. A process of producing a copper-containing catalyst for thehydrogenation of oils and fats, which consists essentially of reactingan aqueous acidic solution with an aqueous alkaline solution containingat least one alkali selected from the group consisting of hydroxides andcarbonates of alkali metals and calcium hydroxide and mixtures thereof,said aqueous acidic solution containing copper ions and ions of a secondmetal selected from the group consisting of Zinc, cadmium, aluminum,silicon, titanium, tin, zirconium, vanadium, chrominum molybdenum,tungsten, manganese, Ag, Sc, Y, La, Ce, Ga, In, Hf, Be, Mg, Ca, Sr, Baand metals of Group VIII of the Mendeleif Periodic Table, the mol ratioof said second metal to copper in said acidic solution being between 1:100 and 70:30, said acidic and alkaline solutions being addedsimultaneously to an aqueous third solution having a pH between 7 to 11to form a combined precipitate of said metals, the rate of adding saidacidic and alkaline solutions to said third aqueous solution being soregulated as to keep the pH of the reaction mixture between x0.5 andx+0.5 (wherein x is from 7 to 11) throughout the entire duration of thereaction, washing the precipitate with water to remove the alkalitherefrom and then drying the same, and roasting the same at atemperature below 350 degrees centigrade, whereby an alkalifreehydrogenation catalyst is obtained.

4. A process of producing a copper-containing catalyst for thehydrogenation of oils and fats, which consists essentially of reactingan aqueous acidic solution with an aqueous alkaline solution containingat least one alkali selected from the group consisting of hydroxides andcarbonates of alkali metals and calcium hydroxide and mixtures thereof,said aqueous acidic solution containing copper ions and ions of a secondmetal selected from the group consisting of zinc, cadmium, aluminum,silicon, titanium, tin, zirconium, vanadium, chromium, molybdenum,tungsten, manganese, Ag, Sc, Y, La, Ce, Ga, In, Hf, Be, Mg, Ca, Sr, Baand metals of Group VIII of the Mendeleff Periodic Table, the mol ratioof said second metal to copper in said acidic solution being between1:100 and 70:30, said acidic and alkaline solutions being addedsimultaneously to an aqueous third solution having a pH between 7 and 11to form a combined precipitate of said metals, blowing air into thereaction mixture to convert the precipitate to an oxide, the rate ofadding said acidic and alkaline solutions to said third aqueous solutionbeing so regulated as to keep the pH of the reaction mixture betweenx0.5 and x+0.5 (wherein x is from 7 to 11) throughout the entireduration of the reaction, washing the precipitate with water to removethe alkali therefrom and then drying the same, whereby an alkali-freehydrogenation catalyst is obtained.

5. A process of producing a copper-containing catalyst for thehydrogenation of oils and fats, which consists essentially of reactingan aqueous acidic solution with an aqueous alkaline solution containingat least one alkali selected from the group consisting of hydroxides andcarbonates of alkali metals and calcium hydroxide and mixtures thereof,said aqueous acidic solution containing copper ions and ions of a secondmetal selected from the group consisting of zinc, cadmium, aluminum,silicon, titanium, tin, Zirconium, vwadium, chromium, molybdenum,tungsten, manganese, Ag, Sc, Y, La, Ce, Ga, In, Hf, Be, Mg, Ca, Sr, Baand metals of Group VIII of the Mendeletf Periodic Table, the mol ratioof said second metal to copper in said acidic solution being between1:100 and 70:30, said acidic and alkaline solutions being addedsimultaneously to an aqueous third solution having a pH between 7 and 11to form a combined precipitate of said metals, the rate of adding saidacidic and alkaline solutions to said third aqueous solution being soregulated as to keep the pH of the reaction mixture between x0.5 andx+05 (wherein x is from 7 to 11) throughout the entire duration of thereaction, boiling the reaction mixture after the reaction is completedto convert the precipitate to an oxide, washing the precipitate withwater to remove the alkali therefrom and then drying the same, wherebyan alkali-free hydrogenation catalyst is obtained.

6. A process of producing a copper-containing catalyst for thehydrogenation of oils and fats, which consists essentially of reactingan aqueous acidic solution with an aqueous alkaline solution containingat least one alkali selected from the group consisting of hydroxides andcarbonates of alkali metals and calcium hydroxide and mix tures thereof,said aqueous acidic solution containing copper ions and ions of a secondmetal selected from the group consisting of Zinc, cadmium, aluminum,silicon, titanium, tin, Zirconium, vanadium, chromium, molybdenum,tungsten, manganese, Ag, Sc, Y, La, Ce, Ga, In, Hf, Be, Mg, Ca, Sr, Baand metals of Group III of the Mendeleif Periodic Table, the mol ratioof said second metal to copper in said acidic solution being between 1:and 70:30, said acidic and alkaline solutions being added simultaneouslyto an aqueous third solution having a pH between 7 and 11 and having aninert carrier suspended therein to form a combined precipitate of saidmetals, the rate of adding said acidic and alkaline solutions to saidthird aqueous solution being so regulated as to keep the pH of thereaction mixture between x-0.5 and x+0.5 (wherein at is from 7 to 11)throughout the entire duration of the reaction, washing the precipitatewith water to remove the alkali therefrom and then drying the same,whereby an alkali-free hydrogenation catalyst is obtained.

'7. A process of producing a copper-containing catalyst for thehydrogenation of oils and fats, which consists es sentially of reactingan aqueous acidic solution with an aqueous alkaline solution containingat least one alkali selected from the group consisting of hydroxides andcarbonates of alkali metals and calcium hydroxide and mixtures thereof,said aqueous acidic solution containing copper ions and nickel ions, themol ratio of nickel to copper in said acidic solution being between1:100 and 5:95, said acidic and alkaline solutions being addedsimultaneously to an aqueous third solution having a pH between 7 and 11to form a combined precipitate of said metals, the rate of adding saidacidic and alkaline solutions to said third aqueous solution being soregulated as to keep the pH of the reaction mixture between x-0.5 andx+0.5 (wherein at is from 7 to 11) throughout the entire duration of thereaction, washing the precipitate with water to remove the alkalitherefrom and then drying the same, whereby an alkali-free hydrogenationcatalyst is obtained.

8. A process of producing a copper-containing catalyst for thehydrogenation of oils and fats, which consists essentially of reactingan aqueous acidic solution with an aqueous alkaline solution containingat least one alkali selected from the group consisting of hydroxides andcarbonates of alkali metals and calcium hydroxide and mixtures thereof,said aqueous acidic solution containing copper ions and ions of a secondmetal selected from the group consisting of zinc, cadmium, aluminum,silicon, titanium, tin, Zirconium, vanadium, chromium, molybdenum,tungsten, manganese, Ag, Sc, Y, La, Ce, Ga, In,

1 5 Hf, Be, Mg, Ca, Sr, Ba and metals of Group VIII of the MendelefiPeriodic Table, the mol ratio of said second metal to copper in saidacidic solution being between 1:100 and 70:30, said acidic and alkalinesolutions being added simultaneously to an aqueous third solution havinga pH between 7 and 11 to form a combined precipitate of said metals, therate of adding said acidic and alkaline solutions to said third aqueoussolution being so regulated as to keep the pH of the reaction mixturebetween x0.5 and x+0.5 (wherein x is from 7 to 11) throughout the entireduration of the reaction, washing the precipitate with Water to removethe alkali therefrom and References Cited by the Examiner 1 UNITEDSTATES PATENTS 2,767,202 10/56 Rottig 252476 X 2,874,129 2/59 Bell252454 2,889,350 6 /59 Horny et al 252-476 X 2,981,751 4/61 Keith et al252--454 X 10 3,123,626 3/64 Kirsch 260409 MAURICE A. BRINDISI, PrimaryExaminer.

1. A PROCESS FO PRODUCING A COPPER-CONTAINING HYDROGENATION CATALYST,WHICH CONSISTS ESSENTIALLY OF REACTING AN AQUEOUS ACIDIC SOLUTION WITHAN AQUEOUS ALKALINE SOLUTION CAPABLE OF REACTING WITH THE ACIDICSOLUTION TO FORM A COPRRECIPITATE OF THE HEREINAFTER MENTIONED METALS,SAID AQUEOUS ACIDIC SOLUTION CONTAINING COPPER IONS AND IONS OF A SECONDMETAL SELECTED FROM THE GROUP CONSISTING OF ZINC, CADMIUM, ALUMINUM,SILICON, TITANIUM, TIN, ZIRCONIUM, VANADIUM, CHROMIUM, MOLYBDENUM,TUNGSTEN, MANGANESE, AG, SC, Y, LA, CE, GA, IN, HF, BE, MG, CA, SR, BA,AND METALS OF GROUP VII OF THE MENDELEEF PERIODIC TABLE, THE MOL RATIOOF SAID SECOND METAL TO COPPER IN SAID ACIDIC SOLUTION BEING BETWEEN1:100 AND 70:30, SAID ACIDIC AND ALKALINE SOLUTION S BEING ADDEDSIMULTANEOUSLY TO AN AQUEOUS THIRD SOLUTION HAVING A PH BETWEEN 7 AND 11TO FORM A COMBINED PRECIPITATE OF SAID METALS, THE RATE OF ADDING SAIDACIDIC AND ALKALINE SOLUTIONS TO SAID THIRD AQUEOUS SOLUTION BEING SOREGULATED AS TO KEEP THE PH OF THE REACTION MIXTURE BETWEEN X-0.4 ANDX+0.5 (WHEREIN X IS FROM 7 TO 11) THROUGHOUT THE ENTIRE DURATION OF THEREACTION, WASHING THE PRECIPITATE WITH WATER TO REMOVE THE ALKALITHEREFROM AND THEN DRYING THE SAME, WHEREBY AN ALKALI-FREE HYDROGENATIONCATALYST IS OBTAINED.